CN1310585C - Fungicidal mixtures - Google Patents

Abstract

The present invention relates to a fungicidal mixture comprising synergistically effective amounts of: (1)2- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl ] -2, 4-dihydro- [1, 2, 4] -triazole-3-thione (Prothioconazole), or a salt or adduct thereof, and at least one other fungicidal component selected from the group consisting of: (2) boscalid, (3) carboxin, (4) Metrafenone, (5) a compound of formula (V), (6) a compound of formula (VI), (7) quindoxine, (8) dithianon, (9) thiram, (10) bigram, (11) cetrimide, (12) cyanamide, (13) a compound of formula (XIII), (14) thiophanate-methyl, (15) carbendazim, (16) metalaxyl, (17) fluoroxas, (18) thiabendazole, (19) quintozene, (20) prochloraz and (21) anthraquinone.

Description

fungicidal mixture

The present invention relates to fungicidal mixtures comprising synergistically effective amounts of the following components:

(1) 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4 of formula I ]-triazole-3-thione (Prothioconazole) or its salt or adduct:

and at least one other fungicidal compound selected from:

(2) Boscalid of formula II:

and

(3) Carboxyl of formula III:

and

(4) Metrafenone of Formula IV:

and

(5) Formula V compound:

and

(6) Formula VI compound:

and

(7) quinoxyfin of formula VII:

and

(8) Dithianon of formula VIII:

and

(9) thiramate of formula IX:

and

(10) Bic of formula X:

and

(11) Cyazofamid of formula XI:

and

(12) cyanoxanil of formula XII:

and

(13) Compound of formula XIII:

and

(14) thiophanate-methyl of formula XIV:

and

(15) Carbendazim of formula XV:

and

(16) Metalaxyl of formula XVI:

and

(17) Fluorobacterium of formula XVII:

and

(18) Tibiline of formula XVIII:

and

(19) pentachloronitrobenzene of formula XIX:

and

(20) Prochloraz of formula XX:

and

(21) Anthraquinones of formula XXI:

In addition, the present invention also relates to a method for controlling harmful fungi using a mixture of compound I and at least one of compounds II-XXI, the use of at least one of compound I and compounds II-XXI in the preparation of such mixtures and Compositions comprising such mixtures.

Prothioconazole of formula I, namely 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4 ]-triazole-3-thiones are already known from WO 96/16048.

WO 98/47367 discloses a number of active compound combinations of Prothioconazole with a large number of other fungicidal compounds.

Boscalids of formula II and their use as crop protection agents are described in EP-B 0 545 099.

Carrots of formula III are known and described in US 3,249,499.

Metrafenones of the formula IV are likewise known and described in EP-A-727141, EP-A 897904, EP-A 899 255 and EP-A-967 196.

Compounds of formula V are described in WO 96/19442.

Compounds of formula VI are described in EP-A-1017670, EP-A-1017671 and DE 19753519.4.

Quinoxylin of formula VII is known from EP-A-0 326 330.

Dithianons of formula VIII are described in GB 857 383.

Thiram of the formula IX is described in DE-A-06 42 532.

Bic of formula X is known from DE-A-22 07 575.

The compound of formula XI is described in PCT/EP/02/00237.

Cyanoxanil of formula XII is described in PCT/EP/01/14785.

Compounds of formula XIII are described in WO 99/56551.

Thioprazine-methyl of the formula XIV is known from DE-A-1930540.

Carbendazim of formula XV is described in US 3,657,443.

Metalaxyl of formula XVI is described in US 4,151,299.

Fluorobacteria of formula XVII are known from EP-A-206 999.

Albiline of formula XVIII is known from US 3,017,415.

Pentachloronitrobenzenes of the formula XIX are described in DE-A-682048.

Prochloraz of formula XX is described in US 3,991,071.

Anthraquinones of formula XXI are described in The Pesticide Manual, 12th Edition (2000), p.39.

It was an object of the present invention to provide mixtures with improved activity against harmful fungi and with a reduced total application rate of active compounds (synergistic mixtures) in order to reduce application rates and improve the activity spectrum of the known compounds I-XXI.

We have found that this object is achieved by mixtures of the prothioconazole defined at the outset with at least one other fungicide. Furthermore, we have also found that simultaneous application of at least one of Compound I and Compounds II-XXI, i.e. together or alone, or sequential application of at least one of Compound I and Compounds II-XXI, provides greater control of harmful fungi than The likely effect of each compound administered alone is better.

2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-tri Azole-3-thiones are known from WO 96-16 048. This compound can exist as a "thione" of the formula:

or in the tautomeric "thiol" form of the following formula:

For simplicity, only the "thione" form is given in each case.

Boscalids of formula II are known from EP-B-0 545 099:

Rumatin of formula III is known from US 3,249,499:

Metrafenone of formula IV is known from EP-A-727 141, EP-A-897 904, EP-A-899 255 and EP-A-967 196:

Compounds of formula V are known from WO 96/19442:

Compounds of formula VI are described in EP-A-1017 670, EP-A-1017 671 and DE 197 535 19.4:

Quinoxylin of formula VII is known from EP-A-0 326 330:

Dithianon of formula VIII is described in GB 857 383:

Thiram of the formula IX is known from DE-A-06 42 532:

Bic of formula X is described in DE-A-22 07 575:

The compound of Formula XI is described in PCT/EP/02/00237:

Cyanoxanil of formula XII is described in PCT/EP/01/14785:

Compounds of formula XIII are described in WO 99/56 551:

Thioprazine-methyl of the formula XIV is described in DE-A-1 930 540:

Carbendazim of formula XV is described in US 3,657,443:

Metalaxyl of formula XVI is described in US 4,151,299:

Fluorobacteria of formula XVII are described in EP-A-206 999:

Albiline of formula XVIII is described in US 3,017,415:

Pentachloronitrobenzene of the formula XIX is described in DE-A-682 048:

Prochloraz of formula XX is described in US 3,991,071:

Anthraquinones of formula XXI are described in The Pesticide Manual, 12th Edition (2000), p. 39:

Preference is given to mixtures of Prothioconazole and Boscalid of formula II.

Preference is also given to mixtures of Prothioconazole with a carcinol of formula III.

Mixtures of Prothioconazole with Metrafenone of formula IV are also preferred.

Furthermore, mixtures of prothioconazole with compounds of the formula V are also preferred.

Furthermore, mixtures of prothioconazole with compounds of the formula VI are also preferred.

In addition, mixtures of prothioconazole and quinoxyfin of formula VII are also preferred.

In addition, mixtures of prothioconazole with dithianon of the formula VIII are also preferred.

Furthermore, mixtures of Prothioconazole with thiram of the formula IX are also preferred.

In addition, mixtures of Prothioconazole with Bic of formula X are also preferred.

In addition, mixtures of Prothioconazole and cyridine of the formula XI are also preferred.

Furthermore, preference is also given to mixtures of Prothioconazole with cyanoxanil of the formula XII.

Furthermore, mixtures of Prothioconazole with compounds of formula XIII are also preferred.

Furthermore, mixtures of Prothioconazole with thiophanate-methyl of the formula XIV are also preferred.

Furthermore, mixtures of Prothioconazole and carbendazim of the formula XV are also preferred.

In addition, mixtures of prothioconazole with metalaxyl of the formula XVI are also preferred.

In addition, mixtures of Prothioconazole with fluoxacids of the formula XVII are also preferred.

In addition, mixtures of Prothioconazole with Albiline of the formula XVIII are also preferred.

In addition, mixtures of Prothioconazole with pentachloronitrobenzene of the formula XIX are also preferred.

In addition, mixtures of Prothioconazole and Prochloraz of formula XX are also preferred.

Furthermore, mixtures of prothioconazole with anthraquinones of the formula XXI are also preferred.

Furthermore, mixtures of Prothioconazole with two other fungicidal compounds of the formula II-XXI are also preferred.

Due to the basic nature of their nitrogen atoms, compounds I can form salts or adducts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamon acid, oxalic acid, alkylsulfonic acid (sulfonic acid having a straight-chain or branched alkyl group with 1-20 carbon atoms), arylsulfonic acid or aryldisulfonic acid (aromatic groups such as phenyl and naphthyl with one or two sulfonic acid groups), alkylphosphonic acid (phosphonic acid with a straight-chain or branched alkyl group with 1 to 20 carbon atoms), arylphosphonic acid or aryl di Phosphonic acids (aromatic groups such as phenyl and naphthyl with one or two phosphonic acid groups), where the alkyl or aryl groups may carry other substituents, e.g. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

Suitable metal ions are especially ions of elements of main group II, especially calcium and magnesium; ions of elements of main group III and IV, especially aluminium, tin and lead; transition groups I to VIII Ions of elements, especially ions of chromium, manganese, iron, cobalt, nickel, copper and zinc; and other ions. Particular preference is given to metal ions of transition group elements of the fourth period. Metals can exist in a variety of valences that they may assume.

When preparing mixtures, the active compounds I to XXI are preferably used in their pure form, to which other active compounds which combat harmful fungi or other pests such as insects, arachnids or nematodes, or which have a herbicidal or growth-regulating effect or fertilizers, may be added.

A mixture of compound I and at least one of compounds II-XXI, or applied simultaneously, i.e. compound I and at least one of compounds II-XXI applied together or separately have significant activity against a wide range of phytopathogenic fungi, The fungus is especially selected from fungi of the classes Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some of them act systemically and are therefore also suitable as foliar- and soil-acting fungicides.

They are effective in various crops such as cotton, vegetable varieties (e.g. cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grasses, oats, bananas, coffee, corn, fruit varieties, rice, rye, soybeans, It is especially important to control a large number of fungi in vines, wheat, ornamentals, sugar cane, and seeds of all kinds.

They are particularly suitable for controlling the following phytopathogenic fungi: Blumeria graminis (powdery mildew) in cereals, Erysiphecichoracearum and Sphaerotheca fuliginea in cucurbits, Apple powdery mildew (Podosphaera leucotricha), grape vine uncinula necator (Puccinia) in cereals, Rhizoctonia (Rhizoctonia) in cotton, rice and turf, grass Ustilago in cereals and sugarcane, Venturia inaequalis (scab) in apples, Helminthosporium in cereals, Septoria tritici in wheat nodorum), Botrytis cinerea (botrytis cinerea) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, rice Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora in hops and cucumbers , the genera Alternaria in vegetables and fruits, the genera Mycosphaerella in bananas, and the genera Fusarium and Verticillium.

Compound I and at least one of compounds II-XIII can be applied simultaneously, ie together or separately, or sequentially, the order of which in the case of separate application usually has no effect on the control result.

Compounds I and II are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and III are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and IV are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and V are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and VI are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and VII are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and VIII are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and IX are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and X are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XI are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XII are generally administered in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XIII are generally administered in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XIV are generally administered in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XV are generally administered in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XVI are generally administered in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XVII are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XVIII are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XIX are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XX are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Compounds I and XXI are generally used in a weight ratio of 20:1 to 1:20, especially 10:1 to 1:10, preferably 5:1 to 1:5.

Depending on the type of effect desired, the application rates of the mixtures according to the invention are especially in the area of crops from 0.01 to 8 kg/ha, preferably from 0.1 to 5 kg/ha, especially from 0.1 to 3.0 kg/ha.

Correspondingly, the compound I is applied at an application rate of 0.01-1 kg/ha, preferably 0.05-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound II are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the compound III is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound IV are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound V are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound VI are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound VII are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound VIII are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, compound IX is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, compound X is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound XI are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound XII are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound XIII are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, compound XIV is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound XV are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, compound XVI is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, compound XVII is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, compound XVIII is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, compound XIX is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, compound XX is applied at an application rate of 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

Correspondingly, the application rates of compound XXI are 0.01-1 kg/ha, preferably 0.02-0.5 kg/ha, especially 0.05-0.3 kg/ha.

For seed treatment, the application rate of the mixture is generally 0.001-250 g/kg seed, preferably 0.01-100 g/kg seed, especially 0.01-50 g/kg seed.

To control phytopathogenic harmful fungi, the application of compound I and at least one of compounds II-XXI alone or in combination or the mixture of compound I and at least one of compounds II-IXXI is carried out before the plants are sown or The seed, plant or soil is sprayed or dusted thereafter or before or after emergence of the plants.

The fungicidal synergistic mixture of the present invention or at least one of Compound I and Compound II-XXI can be formulated, for example, as ready-to-spray solutions, powders and suspensions or highly concentrated aqueous, oily or other suspensions, dispersions, They are in the form of emulsions, oil dispersions, pastes, powders, spreading materials or granules, and can be applied by spraying, atomizing, dusting, broadcasting or pouring. The use forms depend on the intended purpose; in any case it should ensure that the mixture according to the invention is distributed as finely and homogeneously as possible.

The formulations are prepared in a manner known per se, for example by adding solvents and/or carriers. Inert additives such as emulsifiers or dispersants are usually mixed with the formulation.

Suitable surfactants are aromatic sulfonic acids such as lignin-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acids and alkali metal, alkaline earth metal and ammonium salts of fatty acids, alkyl- and alkylarylsulfonic acids Salts of alkyl lauryl ethers and fatty alcohol sulfates and sulfated salts of cetyl-, heptadecan- and stearyl alcohol or glycol ethers of fatty alcohols, condensates of sulfonated naphthalene and its derivatives with formaldehyde , naphthalene or naphthalenesulfonic acid condensate with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol or tributylphenylpolyethylene Glycol ethers, alkylaryl polyether alcohols, isotridecyl alcohols, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, polylauryl alcohol Glycol ether acetates, sorbitol esters, lignosulfite waste or methylcellulose.

Powders, spreading materials and dusts can be prepared by mixing or grinding compound I and at least one of compounds II-XXI or a mixture of compound I and at least one of compounds II-XXI with a solid carrier.

Granules (for example coated, impregnated or homogeneous granules) are usually prepared by binding the active compounds to solid carriers.

Fillers or solid carriers are, for example, mineral earths such as silica, silica gel, silicates, talc, kaolin, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide ; Ground synthetic materials; Fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea; Products of plant origin such as grain flour, bark flour, wood flour and nut shell flour; Cellulose flour or other solid carriers.

The formulations generally comprise from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of at least one of compound I and compounds II-XXI or a mixture of compound I and at least one of compounds II-XXI. The active compounds are used in a purity of 90-100%, preferably 95-100% (according to NMR spectroscopy or HPLC).

Compound I and at least one of the compounds II-XXI, mixtures or corresponding formulations by treating harmful fungi with a fungicidally effective amount of the mixture or in the case of separate application with at least one of the compounds I and the compounds II-XXI , its habitat, or the plants, seeds, soil, areas, materials or spaces in which it is desired to control them.

Application can take place before or after infestation by the harmful fungi.

Application example

The synergistic activity of the mixtures of the invention was confirmed by the following tests:

The active compounds are formulated individually or together as a 10% emulsion in a mixture of 85% by weight of cyclohexanone and 5% by weight of emulsifier and diluted with water to the desired concentration.

Evaluation was carried out by determining the percent infection of the leaf area. These percentages were converted to efficacy. Potency ( W ) was calculated using Abbot's formula as follows:

W＝(1-α/β)·100

α corresponds to the percent fungal infection of the treated plants, and

β corresponds to the percent fungal infection of untreated (control) plants.

An efficacy of 0 indicates that the level of infection in treated plants corresponds to that of untreated control plants; an efficacy of 100 indicates that treated plants are not infected.

The expected potency of an active compound mixture is determined using the Colby formula [R.S. Colby, Weeds (Weeds) 15, 20-22 (1967)] and compared to the observed potency.

Colby's formula: E=x+y-x y/100

E is the expected efficacy in % relative to the untreated control when using a mixture of active compounds A and B at concentrations a and b,

x is the potency of active compound A when used at concentration a, expressed in % relative to the untreated control,

y is the potency of active compound B when applied at concentration b expressed in % relative to the untreated control.

Application Example 1: Activity to Wheat Powdery Mildew Caused by Erysiphe graminis forma specialis tritici

Leaves of potted wheat seedlings of the cultivar "Kanzler" are sprayed to the trickle point with an aqueous formulation of active compound prepared from a stock solution comprising 10% active compound, 85% cyclohexanone and 5% emulsifier. 24 hours after the spray coating had dried, the leaves were dusted with spores of powdery mildew of wheat. The test plants are then placed in a greenhouse at 20-24° C. and 60-90% relative atmospheric humidity. The degree of powdery mildew development was determined visually after 7 days as % infection of the total leaf area.

Measurements of the percentage of diseased leaf area were converted to efficacy in % relative to the untreated control. An efficacy of 0 indicates the same disease level as the untreated control; an efficacy of 100 indicates 0% disease level. The expected potency of the combination of active compounds is determined using the Colby formula above and compared to the observed potency.

Table 1 active compound Concentration of active compound in spray liquid, ppm Potency, % relative to untreated control Control (untreated) (90% infested) 0 Compound I = Prothioconazole 410.25 4200 Compound II = Boscalid 410.250.06 0000 Compound IV = Metrafenone 0.060.015 5330 Compound VI 0.250.06 530

Compound VIII = Dithianon 410.25 00 Compound XI = race seat off 10.250.06 22220

Table 2 Combination of the invention observed efficacy Calculated potency ^* ) Compound I=Prothioconazole+Compound II=Boscalid0.25+4ppm mixture 1:16 19 0 Compound I=Prothioconazole+Compound II=Boscalid1+4ppm Mixture 1:4 92 0 Compound I=Prothioconazole+Compound II=Boscalid0.25+1ppm mixture 1:4 53 0 Compound I=Prothioconazole+Compound II=Boscalid1+0.25ppm mixture 4:1 30 0 Compound I=Prothioconazole+Compound II=Boscalid1+0.06ppm mixture 16:1 19 0 Compound I=Prothioconazole+Compound IV Metrafenone0.25+0.06ppm mixture 4:1 65 53 Compound I=Prothioconazole+Compound IV Metrafenone1+0.06ppm mixture 16:1 65 53 Compound I=Prothioconazole+Compound IV Metrafenone0.25+0.015ppm mixture 16:1 42 30 Compound I=Prothioconazole+Compound VI1+0.25ppm mixture 1:16 65 53 Compound I=Prothioconazole+Compound VI0.25+0.06ppm mixture 4:1 18 0 Compound I=Prothioconazole+Compound VI4+0.25ppm mixture 16:1 88 77 Compound I=Prothioconazole+Compound VIII=Dithianon 0.25+4ppm mixture 1:16 33 0 Compound I = Prothioconazole + Compound VIII = Dithianon 1 + 4ppm mixture 1:4 33 0 Compound I=Prothioconazole+Compound VIII=Dithianon 0.25+0.25ppm mixture 1:1 97 0 Compound I = Prothioconazole + Compound VIII = Dithianon 1 + 0.25ppm mixture 4:1 twenty two 0 Compound I＝Prothioconazole+Compound XI＝Safemate 0.06+1ppm mixture 16:1 56 twenty two Compound I＝Prothioconazole+Compound XI＝Sacetamine 1+0.25ppm mixture 4:1 56 twenty two Compound I＝Prothioconazole+Compound XI＝Sacetamine 1+0.25ppm mixture 4:1 33 twenty two Compound I＝Prothioconazole+Compound XI＝Sacetamine 1+0.06ppm mixture 16:1 twenty two 0

^* ) Potency calculated using Colby's formula

The test results show that the potency observed at all mixing ratios is higher than the potency previously calculated using Colby's formula (from Synerg 176.XLS).

Use example 2: Protective activity against cucumber powdery mildew caused by monofilament husks (Sphaerotheca fuliginea)

The leaves of potted cucumber seedlings of the cultivar "chinese snake" were sprayed at the cotyledon stage to the trickle point with an aqueous formulation of active compound consisting of 10% active compound, 85% cyclohexanone and 5% emulsifier. Stock solution preparation. 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of powdery mildew of cucumber. The plants are then grown for 7 days in a greenhouse at 20-24° C. and 60-80% relative atmospheric humidity. The degree of powdery mildew development was determined visually as % infection of the cotyledon area.

Measurements of the percentage of diseased leaf area were converted to efficacy in % relative to the untreated control. An efficacy of 0 indicates the same disease level as the untreated control; an efficacy of 100 indicates 0% disease level. The expected potency of the combination of active compounds is determined using the Colby formula above and compared to the observed potency.

table 3 active compound Concentration of active compound in spray liquid, ppm Potency, % relative to untreated control Control (untreated) (90% infested) 0 Compound I = Prothioconazole 10.25 7856 Compound II = Boscalid 40.250.06 7800 Compound IV = Metrafenone 0.060.015 00 Compound VI 0.060.015 330

Table 4 Combinations of the invention observed efficacy Calculated potency ^* ) Compound I=Prothioconazole+Compound II=Boscalid0.25+4ppm mixture 1:16 99 90 Compound I=Prothioconazole+Compound II=Boscalid1+0.25ppm mixture 4:1 89 78 Compound I=Prothioconazole+Compound II=Boscalid0.25+0.06ppm mixture 4:1 78 56 Compound I=Prothioconazole+Compound II=Boscalid1+0.06ppm mixture 16:1 94 78 Compound I=Prothioconazole+Compound IV=Metrafenone0.25+0.06ppm mixture 4:1 78 56 Compound I=Prothioconazole+Compound IV=Metrafenone1+0.06ppm mixture 16:1 94 78 Compound I=Prothioconazole+Compound IV=Metrafenone0.25+0.015ppm mixture 16:1 78 56 Compound I=Prothioconazole+Compound VI0.25+0.06ppm mixture 4:1 89 70 Compound I=Prothioconazole+Compound VI 0.25+0.015ppm mixture 16:1 72 56

^* ) Potency calculated using Colby's formula

The test results show that the potency observed at all mixing ratios is higher than the potency previously calculated using Colby's formula (from Synerg 176.XLS).

Claims (6)

1. Fungicidal mixture comprises following component:

(1) 2-[2-of formula I (1-chlorine cyclopropyl)-3-(2-chlorphenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thioketones (Prothioconazole) or its salt or adduct:

With

(2) Boscalid of formula II:

The weight ratio of the Prothioconazole of its Chinese style I and the Boscalid of formula II is 20: 1 to 1: 20.

2. as the desired Fungicidal mixture of claim 1, the weight ratio of the Prothioconazole of its Chinese style I and the described fungicide of formula II is 10: 1 to 1: 10.

3. methods for fighting harmful mushrooms, comprise with as the desired Fungicidal mixture processing of claim 1 harmful fungoid, they the habitat or want to prevent and treat their plant, seed, soil, zone, material or space.

4. as the desired method of claim 3, wherein formula I compound as claimed in claim 1 and formula II compound as claimed in claim 1 are used simultaneously, i.e. associating or use separately or is used successively.

5. as claim 3 or 4 desired methods, wherein use Fungicidal mixture as claimed in claim 1 or formula I compound and formula II compound with the amount of 0.01-8kg/ha.

6. a Fungicidal composition comprises as the desired Fungicidal mixture of claim 1 and solid or liquid-carrier.